Polymer blend comprising fluorinated block copolyester

ABSTRACT

Disclosed are polymer blends prepared by melt blending a fluorinated block copolyester with a non-fluorinated polyester wherein the fluorinated block copolyester comprises blocks of fluoroether modified aromatic polyester and blocks of unmodified polyester. Suitable block copolyesters have a blockiness index, B, in the range of 0.25 to 1.0. Shaped articles prepared from the blends exhibit oil and soil resistance with high fluorine efficiency.

RELATED UNITED STATES PATENT APPLICATIONS

This application is related to co-pending U.S. patent application Ser.No. 13/291,582 submitted as on Nov. 8, 2011, entitled “Process ForPreparing Fluorinated Block Copolyesters;” co-pending U.S. patentapplication Ser. No. 13/291,582 submitted as on Nov. 8, 2011, entitled“Fluorinated Block Copolyesters;” co-pending U.S. patent applicationSer. No. 13/291,673 submitted as on Nov. 8, 2011, entitled “ShapedArticles Comprising a Fluorinated Block Copolyester;” co-pending U.S.patent application Ser. No. 12/873,423 entitled “FluorovinyletherFunctionalized Aromatic Diesters And Derivatives Thereof, and Processfor the Preparation Thereof,” filed on Sep. 1, 2010; and, co-pendingU.S. patent application Ser. No. 12/873,428 entitled “PolyestersComprising Fluorovinylether Functionalized Aromatic Moieties,” filed onSep. 1, 2010.

FIELD OF THE INVENTION

The invention is directed to polymer blends prepared by melt blending afluorinated block copolyester with a non-fluorinated polyester whereinthe fluorinated block copolyester comprises blocks of fluoroethermodified aromatic polyester and blocks of unmodified polyester. Shapedarticles prepared from the blends exhibit oil and soil resistance withhigh fluorine efficiency.

BACKGROUND

Many polymers used in textile fiber applications, including apparel,bedding, and carpets and rugs, are known to exhibit susceptibility tostaining. Polyesters and polyamides are known to exhibit staining fromoily spills. The art discloses a number of surface treatment proceduresand chemicals that have been employed over past decades to impart oiland soil repellency to polyester and polyamide fibers. Some of thesetreatments have been quite successful. However, all such treatments aresubject to degradation from repeated wear—they tend to be graduallywiped off the surface in ordinary use. As a result, the well-knownsurface treatments used in the art tend to lose effectiveness over time,and require restoration. Restoration is a responsibility that devolvesupon the consumer. Failure to regularly restore the surface treatmentleads to premature deterioration of the appearance of the textilearticle to which it had been applied.

It is clear in the art that there is a need to provide oil and soilrepellency of greater durability to polyester and polyamide textilegoods.

Generally, oily substances cause staining in polyesters and polyamidesbecause the oily substance wets the surface, and then diffuses into theinterstices of the fibrous material. Soil repellency technologies havetypically been directed to reducing the surface energy of the fibers toreduce the tendency of oils to wet the surface. It is well-known in theart that fluorinated chemicals are highly effective at reducing thesurface energy of polyester and polyamide textile goods.

Fluorinated chemicals are also expensive, so it is highly desirable thatas high a percentage as possible of the available fluorine atoms becaused to reside on the fiber surface, rather than within the body ofthe fiber where it does no good for soil repellency. In addition, thelower the concentration of additives in a polymer, the higher theproperty retention of the polymer itself. The higher the percentage ofthe fluorine atoms that reside on the surface of the fiber, the higherthe so-called fluorine efficiency. A high fluorine efficiency is highlydesirable.

Yokozawa et al. (Prog. Polym. Sci. 2007, 32, 147) disclose a so-calledchain growth polycondensation process for the manufacturing ofcondensation polymers with defined molecular weights, molecular weightdistributions and selective compositions.

WO2011/028778 discloses poly(alkylene arylate) copolymers comprisingfluoroether functionalized alkylene arylate repeat units. Soil and waterresistant fibers and fabrics prepared therefrom are disclosed.

Several block copolyesters or copolyether esters are in commercial use.Devaux et al., J. Poly Sci, Pol. Phys., 20, 1875 pp (1982); and, Devaux,Chapt. 3, Transreactions in Condensation Polymers, Fakirov, ed., JohnWiley & Sons, DOI: 10.1002/9783527613847, Chapter 3.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a block copolymer having ablockiness index, B, in the range of 0.56 to 0.8, comprising a firstblock comprising a plurality of non-fluorinated alkylene arylate repeatunits adjacent to one another; and a second block comprising a pluralityof fluoroether functionalized alkylene arylate repeat units adjacent toone another; said non-fluorinated alkylene arylate repeat unitrepresented by Structure I

wherein each R is independently H or C₁-C₁₀ alkyl, and R³ is C₂-C₄alkylene which can be branched or unbranched;and, said fluoroether functionalized repeat units are represented byStructure II,

wherein Ar represents a benzene or naphthalene radical; each R isindependently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl; OH, or aradical represented by the Structure (III)

with the proviso that only one R can be OH or the radical represented bythe Structure (III);R¹ is a C₂-C₄ alkylene radical which can be branched or unbranched,X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and, Q represents the Structure (IIa)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

In another aspect, the invention provides a process comprising combiningin the presence of a catalyst a non-fluorinated poly(alkylene arylate)first homopolymer and a fluoroether functionalized poly(alkylenearylate) second homopolymer to form a reaction mixture; heating saidreaction mixture under vacuum to a temperature above the meltingtemperatures of each said homopolymer to prepare a liquified reactionmixture; and, agitating the liquified reaction mixture until the desiredmolecular weight is achieved.

In another aspect, the invention provides a polymer blend comprising apoly(alkylene arylate) and 0.1 to 10 weight percent based upon the totalweight of the blend of a block copolymer having a blockiness index, B,in the range of 0.56 to 0.8, comprising a first block comprising aplurality of non-fluorinated alkylene arylate repeat units adjacent toone another; and a second block comprising a plurality of fluoroetherfunctionalized alkylene arylate repeat units adjacent to one another;said non-fluorinated alkylene arylate repeat unit represented byStructure I

wherein each R is independently H or C₁-C₁₀ alkyl, and R³ is C₂-C₄alkylene which can be branched or unbranched;and, said fluoroether functionalized repeat units are represented byStructure II,

wherein, Ar represents a benzene or naphthalene radical; each R isindependently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl; OH, or aradical represented by the Structure (III)

with the proviso that only one R can be OH or the radical represented bythe Structure (III);R¹ is a C₂-C₄ alkylene radical which can be branched or unbranched,X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the Structure (IIa)

-   -   wherein q=0-10;    -   Y is 0 or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B depict the NMR peaks from the ratios of which theblockiness index, B, of a copolymer is determined.

FIG. 2 depicts the molecular weight distributions of the two lowmolecular weight homopolymers from which a block copolymer according tothe invention is prepared. The molecular weight distribution of theblock copolymer is also shown.

FIG. 3 is a schematic depiction of the fiber spinning apparatus employedin Example 8.

DETAILED DESCRIPTION

When a range of values is provided herein, it is intended to encompassthe end-points of the range unless specifically stated otherwise.Numerical values used herein have the precision of the number ofsignificant figures provided, following the standard protocol inchemistry for significant figures as outlined in ASTM E29-08 Section 6.For example, the number 40 encompasses a range from 35.0 to 44.9,whereas the number 40.0 encompasses a range from 39.50 to 40.49.

Molecular weight of the polyester polymers disclosed herein can bedetermined by any of a variety of methods. One such method commonlyemployed in the art of polyester polymers is the measurement ofso-called intrinsic viscosity. The intrinsic viscosity of a polymer isdetermined by extrapolation of the measured solution viscosity of thepolymer to zero concentration of polymer. The intrinsic viscosity sodetermined can then be related to the weight-average molecular weight(M_(w)) of the polymer by the Mark-Houwink equation, as described inPolymer Chemistry, Charles L. Carraher Jr., 5th edition, Marcel-Dekker(2000)

Another method for determining molecular weight is by so-calledsize-exclusion chromatography (SEC). A suitable method for performingSEC on the polymers is provided infra. SEC has the advantage of definingthe entire molecular weight distribution, whereas intrinsic viscositydefines a single point on that distribution.

The parameters n, p, and q as employed herein are each independentlyintegers in the range of 1-10.

As used herein, the term “copolymer” refers to a polymer comprising twoor more chemically distinct repeat units in the polymer chain, includingdipolymers, terpolymers, tetrapolymers and the like. The term“homopolymer” refers to a polymer wherein the repeat units in thepolymer chain are chemically indistinguishable from one another (withthe possible exception of the end groups). For the sake of brevity andclarity, the present disclosure is directed to copolymers comprising twochemically distinct repeat units. However, the same description can bereadily extended to polymers having more than two chemically distinctrepeat units. The copolymers disclosed herein preferably consistessentially of two chemically distinct repeat units.

In a copolymer comprising a first repeat unit and a second repeat unit,the term “block” in the phrase “block copolymer” refers to a sub-sectionof the copolymer chain in which a plurality of first repeat units areadjacent to one another rather than adjacent to second repeat units. Ina copolymer formed by completely random combination of the two repeatunits, there will result a certain number of blocks, of certain lengthsof each repeat unit. The specific number of blocks and their length willdepend upon the molar ratios of the repeat units, the relativereactivity of the repeat units, and other factors. A block copolymer isone in which the number and size of the blocks exceeds by astatistically significant amount that determined for a random copolymerof similar overall composition.

The blockiness index, B, is defined by Devaux, op. cit., as

$B = \frac{F_{12}}{2{\sum\limits_{i = 1}^{2}F_{i}}}$wherein F₁₂ represents the total mole fraction of diads of first andsecond repeat units, in either sequence, and F_(i) represents the molefraction of repeat units of type “i” and the sum is taken over the twotypes of repeat units. For a 50/50 mol % composition of two polymercomponents B takes a value of 0 for a perfect block copolymer sinceF₁₂=F₂₁≈0, and a value of 1 for a random copolymer since F₁₂=F₂₁≈0.25,in both these cases F₁=F₂≈0.5.

F₁₂, F₂₁, F₁₁, and F₂₂ are the molar fractions of dyad repeat units inthe polymer structure. The different dyads present in the copolymers:

The designation “G” represents the NMR peak of the two OCH₂ carbons whentwo trimethylene terephthalate moieties are adjacent to one another;this dyad is designated TT; its mole fraction is F₁₁. The designation“D” represents the NMR peak of the two OCH₂ carbons when two 3-GF₁₆-iso(or two 3-GF₁₀-iso) moieties are adjacent to one another; this dyad isdenoted FF; its mole fraction F₂₂. The designations “E” and “F”represent the two NMR peaks of the two different OCH₂ groups in the dyadwhich contains both a 3-GF₁₆-iso (or 3-GF₁₀-iso) moiety and atrimethylene terephthalate moiety. There are two statistically possiblearrangements of this dyad, which are equivalent by NMR, designated FTand TF, with mole fractions F₁₂ and F₂₁. The relative amount of the TTdyad is determined by the area of peak G/2, of the FF dyad by the areaof D/2, and of the sum FT and TF dyads by the area of (E+F)/2. Thesedyad amounts can be normalized to 100% to give the mole fraction of eachtype of dyad. Each of the dyad mole fractions is thus determined asfollows:

$F_{i} = \frac{\int X_{i}}{\sum\limits_{j = {1 - 4}}{\int X_{j}}}$In a random copolymer the statistical ratio of the dyad is 1:2:1 forTT:TF+FT:FF. In this case the areas of peaks D, E, F, G will be 1:1:1:1.

A representative NMR is shown in FIG. 1. A random copolymer and a blockycopolymer were prepared to have identical composition. A specimen ofeach was dissolved in deuterated trichloroethylene (TCE-d2), and the ¹³CNMR spectrum determined on a 700 MHz NMR. In the range of 63-62 ppm,four peaks were observed, designated respectively, E, D, G, F. The topset of peaks corresponded to the random copolymer. The bottom set ofpeaks corresponded to the blocky copolymer.

Referring again to FIG. 1, it is clear that in a random copolymer, therelative mole fraction of any one dyad is as probable as that ofanother. However, in the block copolymer, the mole fractionscorresponding to the E and F dyads (F₁₂ and F₂₁) were reduced in favorof higher mole fractions corresponding to the D and G dyads (F₁₁ andF₂₂).

Another way to characterize block copolymers is to compare the molecularweight distributions of the starting oligomeric or low molecular weighthomopolymers with that of the final copolymer. FIG. 2 depicts resultsobtained from size exclusion chromatography employing the methoddescribed infra. In FIG. 2, curves 1 and 2 depict molecular weightdistribution of fluorinated and non-fluorinated homopolymers having aM_(n) of ca. 9,000 D. Curve 3 depicts the molecular weight distributionof the copolymer formed therefrom according to the process. The M_(n) ofthe copolymer was ca. 60,000 D. All three distributions have apolydispersity (M_(w)/M_(n)) of ca. 2.0—the typical characteristic of asingle condensation polymer population. Thus, the copolymer indicatesthat the two low molecular weight homopolymers fully reacted to form asingle higher molecular weight polymer population, and that thecopolymer is a multi-block copolymer.

A block copolymer also presents characteristic thermodynamic properties.Because of the blocky structure along the polymer chain, the blockcopolymer retains some of the features of the separate homopolymers thatconstitute the blocks. The block copolymer has two glass transitiontemperatures that are close to those of the separate homopolymericcomponents, and a melting point that corresponds to that of thenon-fluorinated poly(alkylene arylate) homopolymer component. Incontrast, a random copolymer of the same overall composition exhibitsonly one glass transition temperature that corresponds to neither ofthose of the separate components, and no melting point because therandomized presence of the fluorinated moiety along the polymer chainacts to disrupt the crystallization of the non-fluorinated component.The fluorinated homopolymer is fully amorphous, and doesn't exhibit amelting point.

In one aspect, the present invention provides a copolymer having ablockiness index, B, in the range of 0.56 to 0.8, comprising a firstblock comprising a plurality of non-fluorinated alkylene arylate repeatunits adjacent to one another; and a second block comprising a pluralityof fluoroether functionalized alkylene arylate repeat units adjacent toone another; said non-fluorinated alkylene arylate repeat unitrepresented by Structure I

wherein each R is independently H or C₁-C₁₀ alkyl, and R³ is C₂-C₄alkylene which can be branched or unbranched;and, said fluoroether functionalized repeat units are represented byStructure II,

wherein, Ar represents a benzene or naphthalene radical; each R isindependently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl; OH, or aradical represented by the Structure (III)

with the proviso that only one R can be OH or the radical represented bythe Structure (III);R¹ is a C₂-C₄ alkylene radical which can be branched or unbranched,X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the Structure (IIa)

wherein q=0-10; Y is O or CF₂; Rf¹ is (CF₂)_(n), wherein n is 0-10; and,Rf² is (CF₂)_(p),wherein p is 0-10, with the proviso that when p is 0, Y is CF₂.

As can be noted in the formulas above that show substituents attached toaromatic rings “Ar”, the substituents can be attached to the aromaticrings at any point, thus making it possible to have ortho-, meta- andpara-substituents as defined above.

There is no particular limitation on the relative amount of thefluoroether functionalized repeat units and non-fluorinated repeatunits. The desired amounts will be determined by considerations peculiarto the intended use. In one embodiment of the copolymer, the mole ratioof non-fluorinated repeat units to fluoroether functionalized repeatunits is in the range of 9 to 0.25. In a further embodiment, the moleratio is in the range of 1.5 to 0.67.

In one embodiment of the polymer, each R is H.

In one embodiment of the fluoroether functionalized alkylene arylaterepeat unit, one R is represented by the Structure (II) and theremaining two Rs are each H.

In one embodiment, R¹ is an ethylene radical.

In one embodiment, R¹ is a trimethylene radical, which can be branched.

In one embodiment, R¹ is a tetramethylene radical, which can bebranched.

In one embodiment, X is O. In an alternative embodiment, X is CF₂.

In one embodiment, Y is O. In an alternative embodiment, Y is CF₂.

In one embodiment, Rf¹ is CF₂.

In one embodiment, Rf² is CF₂.

In one embodiment, Rf² is a bond (that is, p=0), and Y is CF₂.

In one embodiment, a=0.

In one embodiment, a=1, q=0, and n=0.

In one embodiment of the fluoroether functionalized alkylene arylaterepeat unit, Ar is a benzene radical, a=1, each R is H, Z is H, R¹ istrimethylene, X is O, Y is O, Rf¹ is CF₂, and Rf² is perfluoropropenyl,and q=1.

In one embodiment the specific repeat unit represented by Structure (I)is represented by the Structure (IVa)

wherein R¹, Z, X, Q, and a are as stated supra.

In an alternative embodiment the specific repeat unit represented byStructure (I) is represented by the Structure (IVb)

wherein R¹, Z, X, Q, and a are as stated supra.

In one embodiment the non-fluorinated alkylene arylate repeat unitcomprising arylate repeat unit is represented by the Structure (V),

wherein R³ is C₂-C₄ alkylene which can be branched or unbranched. In oneembodiment, R³ is trimethylene. In one embodiment, the repeat unitrepresented by Structure (V) is a C₂-C₄ alkylene terephthalate radical,especially a trimethylene terephthalate radical. In an alternativeembodiment, the repeat unit represented by Structure (V) is a C₂-C₄alkylene isophthalate radical, especially a trimethylene terephthalateradical.

The molecular weight of the final copolymer varies depending on theoverall condensation time. Typically a longer overall reaction timeleads to higher overall molecular weight assuming adequate vacuum andstirring conditions can be maintained. In general, molecular weightnumber averages (M_(n)) between 20,000 Da (Intrinsic viscosity I.V.<0.4dL/g) to 100,000 Da (I.V.=0.73 dL/g) was reached.

In one embodiment of the copolymer, the mole ratio of non-fluorinatedrepeat units to fluoroether functionalized repeat units is in the rangeof 9 to 0.25. In a further embodiment, the mole ratio is in the range of1.5 to 0.67.

In another aspect, the invention provides a process comprising combiningin the presence of a catalyst a non-fluorinated poly(alkylene arylate)first homopolymer and a fluoroether functionalized poly(alkylenearylate) second homopolymer to form a reaction mixture; heating saidreaction mixture under vacuum to a temperature above the meltingtemperatures of each said homopolymer to prepare a molten reactionmixture; and, agitating the molten reaction mixture until the desiredmolecular weight is achieved.

In one embodiment, the fluoroether-functionalized poly(alkylene arylate)is an oligomer having a number average molecular weight in the range of5,000 to 15,000 Da.

In one embodiment, both the non-fluorinated poly(alkylene arylate)homopolymer and the fluoroether-functionalized poly(alkylene arylate)homopolymer are oligomers having a number average molecular weight inthe range of 5,000 to 15,000 D.

It has now been found that little transesterification occurs in the meltbetween the fluoroether functionalized homopolymer and thenon-fluorinated homopolymer. Condensation reactions occur at end groupsof the melt-mixed polymers in the presence of a suitable catalyst. Theinternal structure of the homopolymer chains remains substantiallyintact. The product of the reaction is the block copolymer.

The number and size of the blocks in the polymer chain will depend uponthe molecular weight of each of the starting homopolymers. Highmolecular weight homopolymer starting materials will lead to copolymershaving a relatively small number of relatively large blocks, andreaction rate is relatively slow. The molecular weight of the resultingpolymer could be undesirably high for many applications. Low molecularweight homopolymer starting materials result in copolymers with more butrelatively shorter blocks. The resulting copolymers may exhibitundesirably low molecular weight. The molecular weight of the copolymercan be increased by increasing the reaction time, but longer reactiontime also results in more transesterification and greater randomization.

Any non-fluorinated poly(alkylene arylate) homopolymer such as is knownin the art is suitable for use as the non-fluorinated poly(alkylenearylate) homopolymer in the processes disclosed herein. Suitablenon-fluorinated poy(alkylene arylate) homopolymers include, but are notlimited to, poly(ethylene terephthalate) homopolymer, poly(trimethyleneterephthalate) homopolymer, and poly(tetramethylene terephthalate)homopolymer. Suitable non-fluorinated poly(alkylene arylate)homopolymers have a molecular weight, as measured by intrinsic viscosity(I.V.) in the range of 0.1-1.1 dL/g. with 0.3-0.4 dL/g preferred.Suitable non-fluorinated poly(alkylene arylates) can be purchased fromcommercial sources, or produced in a laboratory setup to reach molecularweights outside the commercial range. An aromatic polyester homopolymeris prepared by mixing dimethylterepthalate or terephthalic acid with anexcess of C₂-C₄ alkylene glycol or a mixture thereof, branched orunbranched, and a catalyst to form a reaction mixture. The reaction canbe conducted in the melt, preferably within the temperature range of 180to 240° C., to initially condense either methanol or water, after whichthe mixture can be further heated, preferably to a temperature withinthe range of 230 to 300° C., and evacuated, to remove the excess C₂-C₄glycol and thereby form a homopolymer

Suitable catalysts include but are not limited to titanium (IV)butoxide, titanium (IV) isopropoxide, antimony trioxide, antimonytriglycolate, sodium acetate, manganese acetate, and dibutyl tin oxide.The selection of catalysts is based on the degree of reactivityassociated with the selected glycol. For example, it is known that1,3-propanediol is considerably less reactive than is 1,2-ethanediol.Titanium butoxide and dibutyl tin oxide—both considered “hot”catalysts—have been found to be suitable for process when1,3-propanediol is employed, but are considered over-active for theprocess when 1,2-ethanediol.

The reaction can be carried out in the melt. The resulting polymer canbe separated by vacuum distillation to remove the excess of C₂-C₄glycol.

Preparation of a suitable fluoroether functionalized poly(alkylenearylate) homopolymer is described in WO2011/028778. A fluoroetherfunctionalized aromatic diester or diacid is combined with an excess ofC₂-C₄ alkylene glycol or a mixture thereof, branched or unbranched, anda catalyst to form a reaction mixture. The reaction can be conducted inthe melt, preferably within the temperature range of 180 to 240° C., toinitially condense either methanol or water, after which the mixture canbe further heated, preferably to a temperature within the range of 210to 300° C., and evacuated, to remove the excess C₂-C₄ glycol and therebyform a homopolymer comprising repeat units having the Structure (II),wherein the fluoroether functionalized aromatic diester or diacid isrepresented by the Structure (V),

wherein, Ar represents a benzene or naphthalene radical; each R isindependently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl; OH, or aradical represented by the Structure (III)

with the proviso that only one R can be OH or the radical represented bythe Structure (III); R² is H or C₁-C₁₀ alkyl; X is O or CF₂; Z is H, Cl,or Br; a=0 or 1;and, Q represents the Structure (IIa)

-   -   wherein q=0-10; Y is O or CF₂; Rf¹ is (CF₂)_(n), wherein n is        0-10; and, Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso        that when p is 0, Y is CF₂.

In some embodiments, the reaction is carried out at about the refluxtemperature of the reaction mixture.

In one embodiment of the process, one R is OH.

In one embodiment of the process, each R is H.

In one embodiment of the process, one R is OH and the remaining two Rsare each H.

In one embodiment of the process, one R is represented by the Structure(II) and the remaining two R⁵ are each H.

In one embodiment of the process, R² is H.

In one embodiment of the process, R² is methyl.

In one embodiment of the process, X is O. In an alternative embodiment,X is CF₂.

In one embodiment of the process, Y is O. In an alternative embodiment,Y is CF₂.

In one embodiment of the process, Rf¹ is CF₂.

In one embodiment of the process, Rf² is CF₂.

In one embodiment of the process, Rf² is a bond (that is, p=0), and Y isCF₂.

In one embodiment, a=0.

In one embodiment, a=1, q=0, and n=0.

In one embodiment of the process, each R is H, Z is Cl, R2 is methyl, Xis O, Y is O, Rf1 is CF2, and Rf2 is perfluoropropenyl, and q=1.

Suitable alkylene glycols include but are not limited to 1,2-ethanediol,1,3-propanediol, 1,4-butanediol, and mixtures thereof. In oneembodiment, the alkylene glycol is 1,3-propanediol.

Suitable catalysts include but are not limited to titanium (IV)butoxide, titanium (IV) isopropoxide, antimony trioxide, antimonytriglycolate, sodium acetate, manganese acetate, and dibutyl tin oxide.The selection of catalysts is based on the degree of reactivityassociated with the selected glycol. For example, it is known that1,3-propanediol is considerably less reactive than is 1,2-ethanediol.Titanium butoxide and dibutyl tin oxide—both considered “hot”catalysts—have been found to be suitable for process when1,3-propanediol is employed, but are considered over-active for theprocess when 1,2-ethanediol.

The reaction can be carried out in the melt. The thus resulting polymercan be separated by vacuum distillation to remove the excess of C₂-C₄glycol.

Suitable fluoroether functionalized aromatic diesters can be prepared byforming a reaction mixture comprising a hydroxy aromatic diester in thepresence of a solvent and a catalyst with a perfluoro vinyl compoundrepresented by the Structure (VI)

wherein X is O or CF₂, a=0 or 1; and, Q represents the Structure (IIa)

-   -   wherein q=0-10; Y is O or CF₂; Rf1 is (CF₂)_(n), wherein n is        0-10; Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that        when p is 0, Y is CF₂;        under agitation at a temperature between about −70° C. and the        reflux temperature of the reaction mixture. The reaction mixture        is cooled following reaction.

When a halogenated solvent is employed, the group indicated as “Z” inthe resulting fluoroether aromatic diester represented by Structure (V)is the corresponding halogen. Suitable halogenated solvents include butare not limited to tetrachloromethane, tetrabromomethane,hexachloroethane and hexabromoethane. If the solvent is non-halogenatedZ is H. Suitable non-halogenated solvents include but are not limited totetrahydrofuran (THF), dioxane, and dimethylformamide (DMF).

The reaction is catalyzed by a base. A variety of basic catalysts can beused, i.e., any catalyst that is capable of deprotonating phenol. Thatis, a suitable catalyst is any catalyst having a pKa greater than thatof phenol (9.95, using water at 25° C. as reference). Suitable catalystsinclude, but are not limited to, sodium methoxide, calcium hydride,sodium metal, potassium methoxide, potassium t-butoxide, potassiumcarbonate or sodium carbonate. Preferred are potassium t-butoxide,potassium carbonate, or sodium carbonate.

Reaction can be terminated at any desirable point by the addition ofacid (such as, but not limited to, 10% HCl). Alternatively, when usingsolid catalysts, such as the carbonate catalysts, the reaction mixturecan be filtered to remove the catalyst, thereby terminating thereaction.

Suitable hydroxy aromatic diesters include, but are not limited to,1,4-dimethyl-2-hydroxy terephthalate, 1,4-diethyl-2-5-dihydroxyterephthalate, 1,3-dimethyl 4-hydroxyisophthalate,1,3-dimethyl-5-hydroxy isophthalate, 1,3-dimethyl 2-hydroxyisophthalate,1,3-dimethyl 2,5-dihydroxyisophthalate, 1,3-dimethyl2,4-dihydroxyisophthalate, dimethyl 3-hydroxyphthalate, dimethyl4-hydroxyphthalate, dimethyl 3,4-dihydroxyphthalate, dimethyl4,5-dihydroxyphthalate, dimethyl 3,6-dihydroxyphthalate, dimethyl4,8-dihydroxynaphthalene-1,5-dicarboxylate, dimethyl3,7-dihydroxynaphthalene-1,5-dicarboxylate, dimethyl2,6-dihydroxynaphthalene-1,5-dicarboxylate, or mixtures thereof.

Suitable perfluorovinyl compounds include, but are not limited to,1,1,1,2,2,3,3-heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane,heptafluoropropyltrifluorovinylether, perfluoropent-1-ene,perfluorohex-1-ene, perfluorohept-1-ene, perfluorooct-1-ene,perfluoronon-1-ene, perfluorodec-1-ene, and mixtures thereof.

To prepare a suitable fluoroether functionalized aromatic diester asuitable hydroxy aromatic diester and a suitable perfluovinyl compoundare combined in the presence of a suitable solvent and a suitablecatalyst until the reaction has achieved the desired degree ofconversion. The reaction can be continued until no further product isproduced over some preselected time scale. The required reaction time toachieve the desired degree of conversion depends upon the reactiontemperature, the chemical reactivity of the specific reaction mixturecomponents, and the degree of mixing applied to the reaction mixture.Progress of the reaction can be monitored using any one of a variety ofestablished analytical methods, including, but not limited to, nuclearmagnetic resonance spectroscopy, thin layer chromatography, and gaschromatography.

When the desired level of conversion has been achieved, the reactionmixture is quenched, as described supra. The thus quenched reactionmixture can be concentrated under vacuum, and rinsed with a solvent.Under some circumstances, a plurality of compounds encompassed by theStructure (V) can be made in a single reaction mixture. In such cases,separation of the products thus produced can be effected by any methodknown to the skilled artisan such as, but not limited to, distillationor column chromatography.

If it is desired to employ the corresponding diacid instead of thediester, the thus produced fluoroether functionalized aromatic diestercan be contacted with an aqueous base, preferably a strong base such asKOH or NaOH, at a gentle reflux, followed by cooling to roomtemperature, followed by acidifying the mixture, preferably with astrong acid, such as HCl or H₂SO₄, until the pH is between 0 and 2.Preferably pH is 1. The acidification thus performed causes theprecipitation of the fluoroether functionalized aromatic diacid. Thethus precipitated diacid can then be isolated via filtration andrecrystallization from suitable solvents (e.g., redissolved in a solventsuch as ethyl acetate, and then recrystallized). The progress of thereaction can be followed by any convenient method, including but notlimited to thin layer chromatography, gas chromatography and NMR.

Once the fluoroether functionalized aromatic compound has been thusprepared, it is suitable for use in preparation of the fluoroetherfunctionalized homopolymer for use in the processes disclosed herein,among other potential uses.

In another aspect, the invention provides a polymer blend comprising apoly(alkylene arylate) and 0.1 to 10 weight percent, preferably 0.5-5%,based upon the total weight of the blend of a block copolymer having ablockiness index, B, in the range of 0.56 to 0.8, comprising a firstblock comprising a plurality of non-fluorinated alkylene arylate repeatunits adjacent to one another; and a second block comprising a pluralityof fluoroether functionalized alkylene arylate repeat units adjacent toone another; said non-fluorinated alkylene arylate repeat unitrepresented by Structure I

wherein each R is independently H or C₁-C₁₀ alkyl, and R³ is C₂-C₄alkylene which can be branched or unbranched;and, said fluoroether functionalized repeat units are represented byStructure II,

wherein, Ar represents a benzene or naphthalene radical; each R isindependently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl; OH, or aradical represented by the Structure (III)

with the proviso that only one R can be OH or the radical represented bythe Structure (III); R¹ is a C₂-C₄ alkylene radical which can bebranched or unbranched, X is O or CF₂; Z is H, Cl, or Br; a=0 or 1;and,Q represents the Structure (IIa)

-   -   wherein q=0-10; Y is O or CF₂; Rf¹ is (CF₂)_(n), wherein n is        0-10; and, Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso        that when p is 0, Y is CF₂.

At concentrations of the block copolymer in the blend less than 0.1weight-% (wt-%) no significant beneficial effect is achieved. Atconcentrations of the block copolymer in the blend greater than 10 wt-%,the desirable properties of the poly(alkylene arylate) are suppressed,and poor fluorine efficiency results.

In one embodiment, the poly(alkylene arylate) is a poly(alkyleneterephthalate). Suitable poly(alkylene terephthalates) include, but arenot limited to, poly(ethylene terephthalate), poly(trimethyleneterephthalate), poly(tetramethylene terephthalate), or poly(ethylenenapthalate). In one embodiment, the poly(alkylene terephthalate) ispoly(trimethylene terephthalate)

In one embodiment, poly(trimethylene terephthalate) has an IV of 0.85 to1.1 dL/g. The poly(trimethylene terephthalate) (PTT) having an IV of0.85 to 1.1 dL/g encompasses homopolymers and copolymers containing atleast 70 mole % trimethylene terephthalate repeat units. The preferredPTT contains at least 85 mole %, more preferably at least 90 mole %,even more preferably at least 95 or at least 98 mole %, and mostpreferably about 100 mole %, trimethylene terephthalate repeat units.

The poly(trimethylene terephthalate) can contain minor amounts of othercomonomers, and such comonomers are usually selected so that they do nothave a significant adverse effect on properties. Such other comonomersinclude 5-sodium-sulfoisophthalate, for example, at a level in the rangeof about 0.2 to 5 mole %. Very small amounts of trifunctionalcomonomers, for example trimellitic acid, can be incorporated forviscosity control.

In one embodiment of the copolymer, the mole ratio of non-fluorinatedrepeat units to fluoroether functionalized repeat units is in the rangeof 9 to 0.25. In a further embodiment, the mole ratio is in the range of1.5 to 0.67.

The blend hereto is prepared in a high shear melt mixing process. Anyhigh shear melt mixing process normally employed in the art to preparepolymer blends is suitable This includes use of twin-screw extruders,Farrel continuous mixers, Brabender and Banbury batch mixers, and thelike. In a suitable process, the components are weight loss fed to thefeed zone of a twin-screw extruder in which they are melted andaggressively mixed, followed by extrusion into strands that, afterquenching, are cut into blend pellets suitable for use in a wide varietyof polymer processes.

Alternatively, the melt blend can be fed directly to a metering pump andthence to a spin head for direct melt spinning into melt blend fibers.

The blend is suitable also for the production of extruded films andsheets; and of molded parts such as by compression or injection molding.

The invention is further described and enabled in the following specificembodiments, but is not limited in scope thereto.

EXAMPLES Materials Purchased from Aldrich Chemical Company, and Used asReceived, were

dimethyl terephthalate (DMT)

dimethyl isophthalate (DMI)

titanium(IV) isopropoxide

ethylene glycol

1,4-butanediol

tetrahydrofuran (THF)

dimethyl 5-hydroxyisophthalate

potassium carbonate

Obtained from the Dupont Company and Used as Received, Unless OtherwiseNoted.

Bio-based 1,3-propanediol (Bio-PDO™)1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluorovinyloxy) propane (PPVE)Sorona® Poly(trimethylene terephthalate) (PTT), bright 1.02 IV

Purchased from SynQuest Labs, and Used as Received

1,1,1,2,2,3,3-heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane(PPPVE)

Testing Methods Surface Analysis

Surface contact angles of hexadecane on polymer film were recorded on a.Ramé-Hart Model 100-25-A goniometer (Ramé-Hart Instrument Co) with anintegrated DROPimage Advanced v2.3 software system. 4 μL of hexadecanewas dispensed using a micro syringe dispensing system.

Molecular Weight by Size Exclusion Chromatography

A size exclusion chromatography system Alliance 2695™ from WatersCorporation (Milford, Mass.), was provided with a Waters 414™differential refractive index detector, a multiangle light scatteringphotometer DAWN Heleos II (Wyatt Technologies, Santa Barbara, Calif.),and a ViscoStar™ differential capillary viscometer detector (Wyatt). Thesoftware for data acquisition and reduction was Astra® version 5.4 byWyatt. The columns used were two Shodex GPC HFIP-806M™ styrene-divinylbenzene columns with an exclusion limit of 2×10⁷ and 8,000/30 cmtheoretical plates; and one Shodex GPC HFIP-804M™ styrene-divinylbenzene column with an exclusion limit 2×10⁵ and 10,000/30 cmtheoretical plates.

The specimen was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)containing 0.01 M sodium trifluoroacetate by mixing at 50° C. withmoderate agitation for four hours followed by filtration through a 0.45μm PTFE filter. Concentration of the solution was circa 2 mg/mL.

Data was taken with the chromatograph set at 35° C., with a flow rate of0.5 ml/min. The injection volume was 100 μl. The run time was 80 min.Data reduction was performed incorporating data from all three detectorsdescribed above. 8 scattering angles were employed with the lightscattering detector. No standard for column calibration was involved inthe data processing

Thermal Analysis

Glass transition temperature (T_(g)) and melting point (T_(m)) weredetermined by differential scanning calorimetry (DSC) performedaccording to ASTM D3418-08.

NMR Analysis

¹³C NMR data was acquired on a 700 MHz NMR, using a 10 mm probe:

In a first determination, a 310 mg polymer specimen and 30 mg ofchromium acetyl acetonate (CrAcAc) were dissolved in deuterated 1,1,2,2tetrachloroethylene (TCE-d2) to 3.1 ml total volume with minimalheating. NMR spectra were acquired using an acquisition time of 1 sec,90 degree pulse of about 11 μsec, spectral width of 44.6 kHz, recycledelay of 5 sec, temperature of 120° C., 2500-4500 transients averaged.Data processed typically with exponential line broadening of 0.5-2 hzand zero fill of 512 k. Spectra were referenced to TCE-d2 carbon at 74.2ppm.

In a second determination, a 310 mg polymer specimen and 30 mg of CrAcAcwere dissolved in deuterated 1,1,1,3,3,3-hexafluoro-2-propanol-d2(TCE-d2) to about 2.4 ml total volume with a dmso-d6 capillary insertfor lock. NMR spectra were acquired using acquisition time of 0.64 or 1sec, 90 degree pulse of =11 μsec, spectral width of 44.6 kHz, recycledelay of 5 sec, temperature at 25° C. and 2500-4500 transients averaged.Data processed with Ib of typically 0.5-2 Hz and zero fill of 512 k.Spectra were referenced to DMSO-d6 carbon at 39.5 ppm.

Note Regarding Reactions

In the following examples, when it is stated that the temperature wasraised to some temperature, and the reaction vessel held for some periodof time, it shall be understood that in all cases, unless specificallynoted to have otherwise been the case, the procedure followed was toincrease the set point of the heat bath to the stated temperature, allowthe heat bath to achieve the set-point temperature, and then to hold thereaction vessel for the indicated period of time after the heat bath hadcome to the set point temperature.

It shall further be understood that stirring at the last stated speedwas maintained throughout all steps in the reactions described, unlessexpressly stated otherwise.

Example 1 and Comparative Example A (CE A) Copolymer from oligomers of3-GT and 3-GF₁₆-iso, long polycondensation time A. Synthesis of(dimethyl5-(1,1,2-trifluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)isophthalate(F₁₆-iso)

Anhydrous THF (12 liters) and dimethyl 5-hydroxy-isophthalate (2100 g)were combined under nitrogen in an oil jacketed 22 liter RB flaskequipped with a condenser, mechanical stirrer, pressure equalizingaddition funnel. To this stirred solution was added anhydrous potassiumcarbonate (345 g), followed by1,1,1,2,2,3,3-heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane(4750 g). Ca. 2 liters of additional THF was used to wash all thereagents into the reaction vessel. The resulting mixture was refluxedfor 12.0 hours.

Next day, the cool reaction mixture was filtered, to remove thepotassium carbonate and the resulting solution concentrated viarot-evaporation. The resulting material was fractional vacuum distilledto give three fractions:

Fraction Wt. (g) NMR Analysis 1 130 THF and Product 2 2714 Product 3.2503 ProductRecovered heel: 897 g.

Proton NMR of the reaction at this stage showed almost completeconversion to the desired material. ¹H NMR (CDCl3, ppm))=8.56 (s, 1H,Ar—H), 7.95 (s, 2H, Ar—H), 6.05 (d, 1H, CF2-CFH—O), 3.89 (s, 6H,COO—CH3)

B. Preparation of 3-GF₁₆-iso homopolymer from F₁₆-iso and1,3-propanediol

150 g of the F₁₆-iso prepared in Example 1 Section A and 32 g of1,3-propanediol were charged to an oven-dried 500 mL three necked roundbottom flask equipped with an overhead stirrer and a distillationcondenser. The reactants were stirred under a nitrogen purge at a speedof 50 rpm while the condenser was kept at 23° C. The contents weredegassed three times by evacuating down to a pressure of 100 Torr andrefilling back to atmospheric pressure with N₂ gas. Tyzor®TPT catalyst(45 mg) was added after the first evacuation. The flask was immersedinto a preheated metal bath after the three degassing/repressurizationcycles set at 210° C. and held for 90 minutes while stirring speed wasincreased from 50 to 180 rpm. Following the 90 minute hold, the nitrogenpurge was discontinued and a vacuum ramp was started such that afterabout 60 minutes the vacuum reached a value of 50-60 mTorr. The reactionwas held under vacuum at 50-60 mTorr for an additional 60 minutes withstirring at 180 rpm. The reaction vessel was then removed from the heatsource. The over-head stirrer was stopped and elevated from the floor ofthe reaction vessel. The vacuum was then turned off and the system waspurged with N₂ gas at atmospheric pressure. The thus formed productmixture was allowed to cool to ambient temperature. The product wasrecovered after carefully breaking the glass with a hammer. Yield=88%.

¹H-NMR (CDCl₃) δ: 8.60 (ArH, s, 1H), 8.00 (ArH—, s, 2H), 7.70 (ArH, s,4H), 6.15 (—CF₂—CFH—O—, d, 1H), 4.70-4.50 (COO—CH₂—, m, 4H), 3.95(—CH₂—OH, t, 2H), 3.85 (—CH₂—O—CH₂—, t, 4H), 2.45-2.30 (—CH₂—, m, 2H),2.10 (—CH₂—CH₂—O—CH₂—CH₂—, m, 4H).

Thermal data: T_(g)=5° C. No melting point was observed. M_(n)=9.1×10³Da, M_(w)=16.6×10³ Da

C. Preparation of 3-GT Homopolymer of Dimethylterephthalate and1,3-propanediol

Dimethylterephthalate (150 g), and 1,3-propanediol (105.9 g) werecharged to an oven-dried 500 mL three necked round bottom flask equippedwith an overhead stirrer and a distillation condenser. The reactantswere stirred under a nitrogen purge at a speed of 10 rpm while thecondenser was kept at 23° C. The contents of the flask were degassedthree times by evacuating down to 500 mTorr and refilling back toatmospheric pressure with N₂ gas. Tyzor®TPT catalyst (94 mg) was addedafter the first evacuation. Following the three degassing cycles, theflask was immersed into a preheated metal bath set at 160° C. The solidswere allowed to completely melt at 160° C. for 20 minutes while thestirring speed was slowly increased to 180 rpm. The temperature wasincreased to 210° C. and was held at 210° C. for 90 minutes. After 90minutes at 210° C., the temperature was increased to 250° C. after whichthe nitrogen purge was discontinued, and a vacuum ramp was started suchthat after about 60 minutes the vacuum reached a value of about 60mTorr. After an additional 30 minutes at 250° C. and 60 mTorr, the heatsource was removed. The over-head stirrer was stopped and elevated fromthe floor of the reaction vessel. The vacuum was then turned off and thesystem purged with N₂ gas at atmospheric pressure. The thus formedproduct was allowed to cool to ambient temperature. The product wasrecovered after carefully breaking the glass with a hammer. Yield=85% of3GT polymer.

¹H-NMR (CDCl₃/TFA-d): δ 8.25-7.90 (ArH—, m, backbone), 7.65 (ArH, s,cyclic dimer), 4.75-4.45 (COO—CH₂—, m, backbone), 3.97 (HO—CH₂—R,t-broad, end group), 3.82 (—CH₂—O—CH₂—, t, backbone DPG), 2.45-2.05(—CH₂—, m, backbone).

Thermal data: T_(g)=55° C., T_(m)=230° C. M_(n)=8.5×10³ Da,M_(w)=16.1×10³ Da.

D. Preparation of 3-GF₁₆-iso-co-3-GT copolymer

15.3 g of the 3-GT prepared in Example 1 Section C and 46 g of the3-GF₁₆-iso prepared in Example 1 Section B were charged to an oven-dried250 mL three necked round bottom flask equipped with an overhead stirrerand a distillation condenser kept at 23° C. The contents of the flaskwere degassed once by evacuating down to 150 mTorr and refilling back toatmospheric pressure with N₂ gas. Tyzor®TPT catalyst (18 mg) was addedafter the evacuation and repressurization. The nitrogen purge was thendiscontinued, and a vacuum ramp was started such that after about 30minutes the vacuum reached a value of about 60 mTorr. The flask was thenimmersed into a preheated metal bath set at 250° C., and the contents ofthe flask were allowed to melt and equilibrate for 10 minutes. Stirringwas initiated and slowly increased to 180 rpm, and the molten contentsof the flask were held under stirring for 3 hours in the 250° C. bath.After 3 hours at 250° C., 60 mTorr, and stirring at 180 rpm, the heatsource was removed. The over-head stirrer was stopped and elevated fromthe floor of the reaction vessel. The vacuum was then turned off, andthe system was purged with N₂ gas at atmospheric pressure. The thusformed product was allowed to cool to ambient temperature. The productwas recovered after carefully breaking the glass with a hammer.

Yield was approximately 90% of an opaque product designated3-GF₁₆-iso-co-3-GT.

¹³C-NMR (TCE-d2): δ 62.9 (E) 62.7 (D) 62.4 (G) 62.2 (F); B=0.8.

Thermal data: T_(g1)=18° C., T_(g2)=54° C., T_(m)=219° C. M_(n)=59.0×10³Da, M_(w)=118.5×10³ Da.

CE-A. Copolymerization of Dimethylterephthalate, F₁₆-iso, and1,3-propanediol

Dimethylterephthalate (30.1 g), F₁₆-iso (100 g), and 1,3-propanediol(42.6 g) were charged to an oven-dried 500 mL three necked round bottomflask equipped with an overhead stirrer and a distillation condenserkept at 23° C. The reactants were stirred under a nitrogen purge at aspeed of 50 rpm. The contents were degassed three times by evacuatingdown to 100 Torr and refilling back to atmospheric pressure with N₂ gas.Tyzor®TPT catalyst [40 mg] was added after the first evacuation. Theflask was immersed into a preheated metal bath set at 160° C. The solidswere allowed to completely melt at 160° C. for minutes after which thestirring speed was slowly increased to 180 rpm. The temperature wasincreased to 210° C. and maintained for 90 minutes. After 90 minutes at210° C., the nitrogen purge was discontinued, and a vacuum ramp wasstarted such that after an additional 60 minutes the vacuum reached50-60 mTorr. The reaction was held under stirring 180 rpm for 3 hoursstill at 210° C. after which the reaction vessel was removed from theheat source. The over-head stirrer was stopped and elevated from thefloor of the reaction vessel. The vacuum was then turned off and thesystem purged with N₂ gas at atmospheric pressure. The thus formedproduct was allowed to cool to ambient temperature. The product wasrecovered after carefully breaking the glass with a hammer. Yield=90% ofa clear product.

¹H-NMR (CDCl₃) δ: 8.60 (ArH, s, 1H), 8.15-8.00 (ArH—, m, 2+4H), 7.65(ArH, s, 4H), 6.15 (—CF₂—CFH—O—, d, 1H), 4.70-4.50 (COO—CH₂—, m, 4H),3.95 (—CH₂—OH, t, 2H), 3.85 (—CH₂—O—CH₂—, t, 4H), 2.45-2.30 (—CH₂—, m,2H), 2.10 (—CH₂—CH₂—O—CH₂—CH₂—, m, 4H).

¹³C-NMR (CDCl₃) δ: 62.6 62.4 62.1 62.0; B=1.

Thermal data: T_(g)=23° C. Only one T_(g) was observed. No melting pointwas observed. M_(n)=12.6×10³ Da, M_(w)=24×10³ Da.

Example 2 Copolymer from Oligomers of 3-GT and 3-GF₁₆-iso, ShortPolycondensation Time

The materials produced in Example 1 Sections A, B, and C were employedas described in Example 2 Section D, infra.

D. Preparation of 3-GF₁₆-iso-co-3-GT Copolymer of 3-GF₁₆-iso and 3-GT

15.3 g of the 3-GT prepared in Example 1 Section C, supra, and 46 g ofthe 3-GF₁₆-iso prepared in Example 1 Section B, supra, were charged toan oven-dried 250 mL three necked round bottom flask equipped with anover-head stirrer and a distillation condenser kept at 23° C. Thereaction mass was kept under nitrogen purge. The contents were degassedonce by evacuating down to 150 mTorr and refilling back to atmosphericpressure with N₂ gas. Tyzor®TPT catalyst (18 mg) was added after theevacuation and repressurization. The nitrogen purge was thendiscontinued, and a vacuum ramp was started such that after about 30minutes the vacuum reached a value of about 60 mTorr. The flask was thenimmersed into a preheated metal bath set at 250° C., and the contents ofthe flask were allowed to melt and equilibrate for 10 minutes. Stirringwas initiated and the speed was slowly increased to 180 rpm, and themolten contents of the flask was left under stirring for 60 minutes inthe 250° C. bath. The heat source was then removed. The over-headstirrer was stopped and elevated from the floor of the reaction vessel.The vacuum was then turned off, and the system purged with N₂ gas. Thethus formed product was allowed to cool to ambient temperature. Theproduct was recovered after carefully breaking the glass with a hammer.Yield=95.7% of an opaque product.

¹³C-NMR (TCE-d2) δ 62.9 (E) 62.7 (D) 62.4 (G) 62.2 (F); B=0.63.

Thermal data: T_(g1)=16.8° C., T_(g2)=51° C., T_(m)=222.5° C.M_(n)=31.7×10³ Da, M_(w)=65×10³ Da.

Example 3 Copolymer from 3-GT and 3-GF₁₆-iso Oligomer

The oligomeric 3-GF₁₆-iso prepared in Example 1 Section B was employedin Example 3 Section C, infra.

C. Preparation of 3-GF₁₆-iso-co-3-GT copolymer of 3-GF₁₆-iso and 3-GT

The procedures of Example 1 Section D were replicated except that 15.3 gof Sorona® Bright poly(trimethylene terephthalate) resin (1.02 I.V.available from The Dupont Company, Wilmington, Del.) were substitutedfor the 3-GT oligomer prepared in Example 1 Section C, and the reactionvessel was held at 250° C. for 90 minutes rather than 3 hours.Yield=82.6% of an opaque product.

¹³C-NMR (TCE-d2) δ 62.9 (E) 62.7 (D) 62.4 (G) 62.2 (F); B=0.56.

Thermal data: T_(g1)=17° C., T_(g2)=56.1° C., T_(m)=220.1° C.M_(n)=100.6×10³ Da, M_(w)=199.6×10³ Da.

Example 4 and Comparative Example B (CE B) A. Synthesis of Dimethyl5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalate (F₁₀-iso):I

Anhydrous THF (12 liters) and dimethyl 5-hydroxy-isophthalate (2100 g)were combined under nitrogen in an oil jacketed 22 liter RB flaskequipped with a condenser, mechanical stirrer, pressure equalizingaddition funnel. To this stirred solution was added anhydrous potassiumcarbonate (1035 g), followed by1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluorovinyloxy)propane (3192 g).Ca. 2 liters of additional THF was used to wash all the reagents intothe reaction vessel. The resulting mixture was refluxed for 10.5 hours.

Next day, the cool reaction mixture was filtered, to remove thepotassium carbonate and the resulting solution concentrated viarot-evaporation. The resulting material was fractional vacuum distilledto give three fractions:

Fraction Wt. (g) NMR Analysis 1 102 Mixture of Product and THF 2 2526Product. 3 1167 ProductRecovered Heel: 676 g

Proton NMR of the reaction at this stage showed complete conversion tothe desired material. 1H NMR (CDCl3, ppm))=8.54 (s, 1H, Ar—H), 7.97 (s,2H, Ar—H), 6.07 (d, 1H, CF2-CFH—O), 3.89 (s, 6H, COO—CH3)

B. Preparation of homopolymer (3-GF₁₀-iso)

150 g of the F₁₀-iso prepared in Example 4 Section A, supra, and 43.1 gof 1,3-propanediol were charged to an oven-dried 500 mL three neckedround bottom flask equipped with an overhead stirrer and a distillationcondenser kept at 23° C. The reactants were stirred under a nitrogenpurge at a speed of 50 rpm. The contents were degassed three times byevacuating down to 100 Torr and refilling back to atmospheric pressurewith N₂ gas. Tyzor®TPT catalyst (45 mg) was added after the firstevacuation. The flask was then immersed into a preheated metal bath setat 160° C. and held for 20 minutes while slowly increasing the stirringspeed to 180 rpm after which the temperature was increased to 210° C.and the reaction flask was held for an additional 90 minutes still at180 rpm. Following the 90 minute hold, the nitrogen purge wasdiscontinued and a vacuum ramp was started such that after about 60minutes the vacuum reached a value of 50-60 mTorr. The reaction was heldfor an additional 90 minutes with stirring at 180 rpm. The heat sourcewas then removed. The over-head stirrer was then stopped and elevatedfrom the floor of the reaction vessel. The vacuum was then turned off,and the system was purged with N₂ gas. The thus formed product wasallowed to cool to ambient temperature. The product was recovered aftercarefully breaking the glass with a hammer. Yield=82.6%.

¹H-NMR (CDCl₃) δ: 8.60 (ArH, s, 1H), 8.00 (ArH—, s, 2H), 7.70 (ArH, s,4H), 6.15 (—CF₂—CFH—O—, d, 1H), 4.70-4.50 (COO—CH₂—, m, 4H), 3.95(—CH₂—OH, t, 2H), 3.85 (—CH₂—O—CH₂—, t, 4H), 2.45-2.30 (—CH₂—, m, 2H),2.10 (—CH₂—CH₂—O—CH₂—CH₂—, m, 4H).

Thermal data: T_(g)=22.6° C. No melting point was observed.M_(n)=17.1×10³ Da, M_(w)=21.2×10³ Da.

C. Preparation of 3-GF₁₀-iso-co-3-GT copolymer of 3-GF₁-iso and 3-GT

20 g of the 3-GT polymer prepared in Example 1 Section C and 46 g of the3-GF₁₀-iso prepared in Example 4 Section B were charged to an oven-dried250 mL three necked round bottom flask equipped with an overhead stirrerand a distillation condenser kept at 23° C. The reaction mass was keptunder N₂ purge atmosphere. The contents were degassed once by evacuatingthe reaction flask down to 150 mTorr and refilling back to atmosphericpressure with N₂ gas. Tyzor®TPT catalyst (20 mg) was added after theevacuation and repressurization. The nitrogen purge was thendiscontinued, and a vacuum ramp was started such that after about 30minutes the vacuum reached a value of about 60 mTorr. The reaction flaskwas then immersed into a preheated metal bath set at 250° C. and thecontents of the reaction flask were allowed to melt and equilibrate for10 minutes. Stirring was initiated and speed was slowly increased to 180rpm. The thus formed melt was left under vacuum with stirring for 15minutes. The heat source. was then removed. The over-head stirrer wasthen stopped and elevated from the floor of the reaction vessel. Thevacuum was turned off, and the system was purged with N₂ gas. The thusformed product was allowed to cool to ambient temperature. The productwas recovered after carefully breaking the glass with a hammer. Yield91.2% of turbid product.

¹³C-NMR (TCE-d2) δ 62.9 (E) 62.7 (D) 62.4 (G) 62.2 (F); B=0.56.

Thermal data: T_(g1)=28.1° C., T_(g2)=51.8° C., T_(m)=216° C.M_(n)=40.6×10³ Da, M_(w)=64.3×10³ Da.

CE-B. Copolymer of Dimethylterephthalate, F₁₀-iso, and 1,3-propanediol

12.2 g of dimethylterephtalate, 30 g of the F₁₀-iso prepared in Example4 Section A, supra, and 17.25 g of 1,3-propanediol were charged to anoven-dried 500 mL three necked round bottom flask equipped with anoverhead stirrer and a distillation condenser kept at 23° C. Thereactants were stirred under a nitrogen purge at a speed of 50 rpm. Thecontents were degassed three times by evacuating down to 100 Torr andrefilling back to atmospheric pressure with N₂ gas. Tyzor®TPT catalyst(13 mg) was added after the first evacuation. The reaction flask wasimmersed into a preheated metal bath set at 160° C. The solids wereallowed to completely melt at 160° C. for 20 minutes, after which thestirring speed was slowly increased to 180 rpm. The temperature wasincreased to 210° C. and maintained for 60 minutes. After 60 minutes,the nitrogen purge was discontinued, and a vacuum ramp was started suchthat after an additional 60 minutes the vacuum reached 50-60 mTorr. Asthe vacuum stabilized, the stirring speed was increased to 225 rpm andthe reaction held for 3 hours. The heat source was then removed. Theover-head stirrer was stopped and elevated from the floor of thereaction vessel. The vacuum was then turned off and the system waspurged with N₂ gas at atmospheric pressure. The thus formed product wasallowed to cool to ambient temperature. The product was recovered aftercarefully breaking the glass with a hammer. Yield=90% of clear product.

¹H-NMR (CDCl₃) δ: 8.60 (ArH, s, 1H), 8.15-8.00 (ArH—, m, 2+4H), 7.65(ArH, s, 4H), 6.15 (—CF₂—CFH—O—, d, 1H), 4.70-4.50 (COO—CH₂—, m, 4H),3.95 (—CH₂—OH, t, 2H), 3.85 (—CH₂—O—CH₂—, t, 4H), 2.45-2.30 (—CH₂—, m,2H), 2.10 (—CH₂—CH₂—O—CH₂—CH₂—, m, 4H).

¹³C-NMR (CDCl₃) δ: 62.6 62.4 62.1 62.0; B=1.

Thermal data: T_(g)=34° C. Only one T_(g) was observed. No melting pointwas observed. M_(n)=129.7×10³ Da, M_(w)=212×10³ Da.

Example 5 Copolymer from Oligomers of 4-GT and 3-GF₁₆-iso

The 3-GF₁₆-iso prepared in Example 1 Section B was employed herein.

C. Preparation of Homopolymer of Dimethylterephthalate and1,4-Butanediol (4-GT)

Example 1 Section C was repeated except that 129.4 g ofdimethylterephthalate instead of 150 g thereof, 118.9 g of1,4-butanediol were used in place of the 105.9 g of 1,3-propanediol, and165 mg of Tyzor® TPT were used instead of the 94 mg thereof employed inExample 1.

Yield=79%. ¹H-NMR (CDCl₃/TFA-d): δ 8.25-7.95 (ArH—, m, backbone),4.70-4.30 (COO—CH₂—, m, backbone), 2.20-1.80 (—CH₂—, m, backbone).Thermal data: T_(g)=42.4° C., T_(m)=223° C. M_(n)=10.9×10³ Da,M_(w)=19.2×10³ Da.

D. Preparation of Copolymer (3-GF₁₆-iso-co-4-GT)

Example 1 Section D was repeated except that 20 g of the 4-GThomopolymer prepared in Example 5 Section C were substituted for the15.3 g of 3-GT in Example 1, 59.4 g of the 3-GF₁₆-iso prepared inExample 1 Section B were used instead of the 46 g used in Example 1Section D, 23 mg of Tyzor® TPT was used instead of the 18 mg used inExample 1 Section D, and the reaction vessel was held for 2 hours at250° C. instead of 3 hours as in Example 1 Section D.

Yield=91.9% of an opaque product.

¹³C-NMR (TCE-d2): δ 62.8 (E) 62.6 (D) 62.6 (G) 62.4 (F); B=0.65.

Thermal data: T_(g1)=11.1° C., T_(g2)=47.2° C., T_(m)=206.8° C.M_(n)=86.6×10³ Da, M_(w)=208.6×10³ Da.

Example 6 Copolymer from Oligomers of 2-GT and 3-GF₆-iso

The 3-GF₁₆-iso prepared in Example 1 Section B was employed herein.

C. Preparation of Copolymer of Dimethylterephthalate,Dimethylisophthalate and Ethyleneglycol (2-GT)

Example 1 Section C was repeated except that: a combination of 145.5 gof dimethylterephthalate and 3.9 g of dimethylisophthalate were used inplace of the 150 g of dimethylterephthalate; 95.6 g of 1,2-ethanediolwere used in place of the 105.9 g of 1,3-propanediol; and, the metalbath was set to 260° C. instead of 250° C. Yield=55%.

¹H-NMR (CDCl₃/TFA-d): δ 8.60 (ArH, s, 1H), 8.25-7.95 (ArH—, m,backbone), 4.80-4.45 (COO—CH₂—, m, backbone).

Thermal data: T_(g)=81.5° C., T_(m)=248.9° C. M_(n)=14.1×10³ Da,M_(w)=27.1×10³ Da.

D. Preparation of Copolymer 3-GF₁₆-iso-co-2-GT

Example 1 Section D was repeated except that 20 g of the 2-GT polymerprepared in Example 6 Section C was substituted for the 15.3 g of the3-GT in Example 1 Section D, 68 g of the 3-GF₁₆-iso was used in place ofthe 46 g thereof in Example 1 Section D, 26 mg of Tyzor® TPT was addedinstead of 18 mg thereof, the bath temperature was 270° C. instead of250° C. as in Example 1 Section D, and the reaction time was 2 hours at270° C., 60 mTorr, with stirring at 180 rpm instead of 3 hours at 250°C. with stirring at 180 rpm as in Example 1 Section D. Yield=93% of anopaque product.

¹³C-NMR (TCE-d2): δ 63.4 (E) 63.2 (D) 62.6 (G) 62.4 (F); B=0.61.

Thermal data: T_(g1)=15.5° C., T_(g2)=77.3° C., T_(m)=217.9° C.M_(n)=76.6×10³ Da, M_(w)=215.4×10³ Da.

Examples 7-9 and Comparative Examples C-E

The 3-GF₁₆-iso-co-3-GT copolymer of Example 1 and the copolymer of CE-Awere separately chopped into one inch sized pieces that were placed inliquid nitrogen for 5-10 minutes, followed by charging to a Wiley millfitted with a 6 mm screen. Each sample was milled at ca. 1000 rpm toproduce coarse particles having a maximum dimension of about ⅛″. Theparticles were dried under vacuum and allowed to warm to ambienttemperature.

The two batches of particles were dried overnight in a vacuum oven atambient temperature under a slight nitrogen purge. Sorona® Bright (1.02dl/g IV) poly(trimethylene terephthalate) (PTT) pellets available fromthe DuPont Company were dried overnight in a vacuum oven at 120° C.under a slight nitrogen purge. Blends of each of the copolymers with theSorona® were prepared in a DSM microcompounder at 1, 2.5, and 5% byweight of the particles with respect to the total weight of the blends.The DSM system is a PC controlled 15 cubic centimeter (cc), co-rotating,intermeshing (self wiping), 2-tipped, conical twin-screw machine with arecirculation loop, discharge valve, nitrogen purge system, and withthree different heating zones. 250° C. was used for all three heatzones. Polymer melt temperature was in the range of 230-235° C. Undernitrogen Sorona® and the respective copolymer were charged and stirredat a speed of 150 rpm for a total mixing time of 5 minutes. Followingthe mixing time, the discharge valve was opened and an extruded one inchwide, 0.015 inch thick, 10 foot long sheet collected. Advancing andreceding surface contact angles of hexadecane were determined asdescribed supra. Results are shown in Table 1 below. Also shown in Table1 is the contact angle for an unblended film of Sorona® Bright PTT.

TABLE 1 Copolymer Hexadecane Concentration Contact Angle (deg.) Example(Wt-%) Advancing Receding 7 1 46.3 37.0 8 2.5 61.6 40.9 9 5 68.5 42.2CE-C 1 39.0 23.0 CE-D 2.5 54.7 33.6 CE-E 5 66.0 43.4 Sorona ® 0 <10(fully Bright wetted)

Examples 8 and 9; Comparative Examples C and D A. Milling

Additional ⅛″ particles were prepared of the 3-GF₁₆-iso-co-3-GTcopolymer prepared in Example 1 Section D by following the proceduresdescribed in Example 7 Section A.

B. Preparation of a Polymer Blend

Sorona® Bright (1.02 dl/g IV) poly(trimethylene terephthalate) (PTT)pellets available from the DuPont Company were dried overnight in avacuum oven at 120° C. under a slight nitrogen purge. The3-GF₁₆-iso-co-3-GT copolymer particles prepared in Example 1 Section Dabove were dried overnight in a vacuum oven at ambient temperature undera slight nitrogen purge. Prior to melt compounding the thus driedparticles of 3-GF₁₆-iso-co-3-GT and pellets of Sorona® Bright werecombined together to form a batch with a concentration of 2 wt-% of the3-GF₁₆-iso-co-3-GT copolymer based upon the total weight of the blend.The thus combined particles and pellets were mixed in a plastic bag byshaking and tumbling by hand.

The thus mixed batch was placed into a K-Tron T-20 (K-Tron ProcessGroup, Pittman, N.J.) weight loss feeder feeding a PRISM laboratoryco-rotating twin screw extruder (available from Thermo FisherScientific, Inc.) equipped with a barrel having four heating zones and adiameter of 16 millimeter fitted with a twin spiral P1 screw. Theextruder was fitted with a ⅛″ diameter circular cross-Section singleaperture strand die. The nominal polymer feed rate was 3-5 lbs/hr. Thefirst barrel Section was set at 230° C. and the subsequent three barrelSections and the die were set at 240° C. The screw speed was set at 200rpm. The melt temperature of the extrudate was determined to be 260° C.by inserting a thermocouple probe into the melt as it exited the die.The thus extruded monofilament strand was quenched in a water bath. Airknives dewatered the strand before it was fed to a cutter that slicedthe strand into about 2 mm length blend pellets.

C. Melt Spinning

Referring to FIG. 3, the blended pellets of polymer thus made, 301, werecharged to a steel cylinder, 302, and topped of with a Teflon® PTFEplug, 303. A hydraulically driven piston, 304, compressed the particles,301, into a melting zone provided with a heater and heated to 260° C.,305, where a melt, 306, was formed, and the melt then forced into aseparately heated, 307, round cross-Section single-hole spinneret (0.012inches in diameter, 0.036 inches in length), 308, heated to 265° C.Prior to entering the spinneret, the polymer passed through a filterpack, not shown. The melt was extruded into a single strand of fiber,309, at a rate of 0.8 g/min. The extruded fiber was passed through atransverse air quench zone, 310, and thence to a wind-up, 311. Two fibersamples were prepared, one at a wind-up speed of 700 m/min (Example 8)and one at a wind-up speed of 1430 m/min. Control fibers of Sorona®Bright were also spun under conditions identical to those of Examples 8and 9 respectively (Comparative Examples C and D). In each case, thesingle filament strands were spun for 30 minutes, and in each case thefilament spun smoothly without breaks. The resulting fiber in each casewas flexible and strong as determined by pulling and twisting by hand.

We claim:
 1. A polymer blend comprising a poly(alkylene arylate) and 0.1to 10 weight percent based upon the total weight of the blend of a blockcopolymer having a blockiness index, B, in the range of 0.56 to 0.8,comprising a first block comprising a plurality of non-fluorinatedalkylene arylate repeat units adjacent to one another; and a secondblock comprising a plurality of fluoroether functionalized alkylenearylate repeat units adjacent to one another; said non-fluorinatedalkylene arylate repeat unit represented by Structure I

wherein each R is independently H or C1-C10 alkyl, and R3 is C2-C4alkylene which can be branched or unbranched; and, said fluoroetherfunctionalized repeat units are represented by Structure II,

wherein, Ar represents a benzene or naphthalene radical; each R isindependently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl; OH, or aradical represented by the Structure (III)

with the proviso that only one R can be OH or the radical represented bythe Structure (III); R¹ is a C₂-C₄ alkylene radical which can bebranched or unbranched, X is O or CF₂; Z is H, Cl, or Br; a=0 or 1; and,Q represents the Structure (IIa)

wherein q=0-10; Y is O or CF₂; Rf¹ is (CF₂)_(n), wherein n is 0-10; and,Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when p is 0,Y is CF₂.
 2. The polymer blend of claim 1 wherein the poly(alkylenearylate) is poly(trimethylene terephthalate).
 3. The polymer blend ofclaim 1 wherein the block copolymer R¹ is an ethylene radical.
 4. Thepolymer blend of claim 1 wherein the block copolymer R¹ is atrimethylene radical, which can be branched.
 5. The polymer blend ofclaim 1 wherein the block copolymer R¹ is a tetramethylene radical,which can be branched.
 6. The polymer blend of claim 1 wherein the blockcopolymer each R is H.
 7. The polymer blend of claim 1 wherein the blockcopolymer the fluoroether functionalized alkylene arylate repeat unit,Ar is a benzene radical, a=1, each R is H, Z is H, R1 is trimethylene, Xis O, Y is O, Rf¹ is CF₂, and Rf² is (CF₂)₃, and q=1.
 8. The polymerblend of claim 1 wherein the block copolymer the fluoroetherfunctionalized alkylene arylate repeat unit is represented by theStructure (IVb)


9. The polymer blend of claim 8 wherein a=1, Z is H, R¹ is trimethylene,X is O, Y is O, Rf¹ is CF₂, and Rf² is (CF₂)₃, and q=1.
 10. The polymerblend of claim 1 wherein the block copolymer R³ is trimethylene.
 11. Thepolymer blend of claim 1 wherein the block copolymer the non-fluorinatedrepeat unit represented by Structure I is a trimethylene terephthalatediradical.
 12. The polymer blend of claim 1 wherein the block copolymeris a multi-block copolymer.
 13. The polymer blend of claim 1 wherein theblock copolymer the non-fluorinated alkylene arylate repeat units andthe fluoroether functionalized alkylene arylate repeat units are eachpresent at a molar concentration, and wherein further, the mole ratio ofnon-fluorinated repeat units to fluoroether functionalized repeat unitsis in the range of 1.5 to 0.67.